Electron spin resonance (ESR) analysis of (100)Si/SiO
/ZrO2, (100)Si/Al2O3 and Si/HfO2 structures with nm-thin dielectric layers deposited by different chemical vapor deposition procedures reveals, after hydrogen detachment, the presence of the trivalent Si dangling-bond-type centers Pb0, Pb1 as prominent defects in all entities. This Pb0, Pb1 fingerprint, generally unique for the thermal (100)Si/SiO2 interface, indicates that the as-deposited (100)Si/metal oxides interface is basically Si/SiO2-like. Though sensitive to the deposition process, the Pb0 density is found to be substantially larger than in standard (100)Si/SiO2. As probed by the Pb- type center properties, the Si/dielectric interfaces of all structures are under enhanced (unrelaxed) stress, typical for low temperature Si/SiO2 growth. Standard quality thermal Si/SiO2 properties in terms of Pb signature may be approached by appropriate annealing (≥ 650°C) in vacuum in the case of (100)Si/SiO
/ZrO2. Yet, O2 ambient appears required for Si/Al2O3 and Si/HfO2. It appears that Si/high-κ metal oxide structures with device grade quality interfaces can be realized with sub-nm thin SiO
interlayers. The density of fast interface states closely matches the Pb0 density variations, suggesting the center as the dominant fast interface trap. They may be efficiently passivated in H2 at 400 °C.